Composition for making coated yarn

ABSTRACT

An aqueous composition is used to clad yarn cores to provide unique coated yarns. This aqueous composition contains: (i) porous particles present in an amount of at least 2 weight % and up to and including 10 weight %, each porous particle comprising a continuous polymeric phase and discrete pores dispersed within the continuous polymeric phase, the porous particles having a mode particle size of 2-50 μm; (ii) a film-forming binder material having a Tg of less than or equal to 25° C., that is present in an amount of 25-60 weight %; (iii) an inorganic filler material having a value of less than 5 on the MOHS scale of mineral hardness, in an amount of at least 2-15 weight %; and (iv) an aqueous medium in an amount of at least 35 weight % in which the film-forming binder material is soluble or dispersible.

RELATED APPLICATIONS

Reference is made to the following copending and commonly assignedpatent applications:

U.S. Ser. No. 16/203,708, filed on Nov. 29, 2018, by Nair, Brick, andSedita, and entitled “Yarn with Coating over Yarn Core”;

U.S. Ser. No. 16/203,722, filed on Nov. 29, 2018, by Sedita, Nair, andBrick, and entitled “Fabric Substrates”; and

U.S. Publication No. 20180223474, filed Apr. 3, 2018 by Nair, Brick, andSedita, the disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to an aqueous composition that can be appliedcoaxially over a yarn core to provide unique coated yarns that can bewoven into fabric substrates that are useful as textiles for controllinglight and heat transmission, for applications such as window shades.Each coated yarn consists of a yarn core that is clad with the aqueouscoating having porous particles, a film-forming binder material, and aninorganic filler material. This coating provides a bright white andopaque appearance as well as heat and light control properties and colorwhere required for the fabric substrates.

BACKGROUND OF THE INVENTION

In general, when light strikes a surface, some of it may be reflected,some absorbed, some scattered, and the rest transmitted. Reflection canbe diffuse, such as light reflecting off a rough surface such as a whitewall, in all directions, or specular, as in light reflecting off amirror at a definite angle. An opaque substance transmits almost nolight, and therefore reflects, scatters, or absorbs all of it. Bothmirrors and carbon black are opaque. Opacity depends on the frequency ofthe light being considered. The visual appearance of an individual fiberis also similarly determined by its optical properties namely itsinteractions with light.

High efficiency window treatments (shades or screens) are designed forheat and glare control for a chosen color. Materials having suchproperties are marketed by MERMET as E-Screen materials havingKOOLBLACK™ Technology.

Such materials can be designed using yarns having a multifilament corethat can be clad or coated with flame a retardant polymeric plastisol orother chemicals, for example as described in EP Patent 0 900 294B1(Damour et al.) and U.S. Pat. No. 9,920,458 (MERMET). For example, themultifilament core can be composed on multiple strands of fiberglass andclad with a poly(vinyl chloride) plastisol can also contain inorganicflame retardants such as zinc borate, or oxides or aluminum, magnesium,zinc, tin, and lead.

One use for such fabrics is as window shades especially for commercialsites. Synthetic woven fabric consisting of bonded PVC-coated polyesterand fiberglass yarns are also described in U.S. Pat. No. 4,587,997(Brooks) and U.S. Pat. No. 6,032,454 (Damour et al.). Fiberglass coreyarns with plastic coatings can provide durability and dimensionalstability.

U.S. Pat. No. 7,754,409 (Nair et al.), U.S. Pat. No. 7,887,984 (Nair etal.), U.S. Pat. No. 8,252,414 (Putnam et al.), and U.S. Pat. No.8,329,783 (Nair et al.) describe porous polymer particles that are madeby a multiple emulsion process, wherein the multiple emulsion processprovides formation of individual porous particles comprising acontinuous polymer phase and multiple discrete internal pores, and suchindividual porous particles are dispersed in an external aqueous phase.The described Evaporative Limited Coalescence (ELC) process is used tocontrol the particle size and distribution while a hydrocolloid isincorporated to stabilize the inner emulsion of the multiple emulsionthat provides the template for generating discrete pores within theresulting porous particles.

Despite the advances provided in the technical field of yarns andtextiles produced therefrom, there is a need for improving their visualappearance by providing greater opacity and light scattering at the yarnlevel and for reducing glare of the final woven fabric made from suchyarns. There is also a need to provide more environmentally friendlyformulations for sheathing/cladding yarns.

SUMMARY OF THE INVENTION

The present invention provides an aqueous composition comprising:

(i) porous particles present in an amount of at least 2 weight % and upto and including 10 weight %, each porous particle comprising acontinuous polymeric phase and discrete pores dispersed within thecontinuous polymeric phase, the porous particles having a mode particlesize of at least 2 μm and up to and including 50 μm;

(ii) a film-forming binder material having a T_(g) of less than or equalto 25° C., which film-forming binder material is present in an amount ofat least 25 weight % and up to and including 60 weight %;

(iii) an inorganic filler material having a value of less than 5 on theMOHS scale of mineral hardness, which non-abrasive, whitening inorganicfiller material is present in an amount of at least 2 weight % and up toand including 15 weight %; and

(iv) an aqueous medium in an amount of at least 35 weight % in which thefilm-forming binder material is soluble or dispersible,

wherein the amounts of the (i) porous particles, the (ii) film-formingbinder material, the (iii) inorganic filler material, and the (iv)aqueous medium are based on the total weight of the aqueous composition.

In some embodiments, the aqueous composition consists essentially of:

(i) porous particles present in an amount of at least 2 weight % and upto and including 10 weight %, each porous particle comprising acontinuous polymeric phase and discrete pores dispersed within thecontinuous polymeric phase, the porous particles having a mode particlesize of at least 3 μm and up to and including 30 μm;

(ii) a film-forming binder material having a T_(g) of less than or equalto 0° C., which film-forming binder material is water-soluble orwater-dispersible, and is present in an amount of at least 25 weight %and up to and including 60 weight %;

(iii) a non-abrasive, whitening inorganic filler material having a valueof less than 5 on the MOHS scale of mineral hardness, whichnon-abrasive, whitening inorganic filler material comprises zinc sulfideand is present in an amount of at least 2 weight % and up to andincluding 15 weight %; and

(iv) an aqueous medium in an amount of at least 35 weight %, andcomprises water in an amount of at least 80 weight % based on the weightof total solvents,

wherein the amounts of the (i) porous particles, the (ii) film-formingbinder material, the (iii) non-abrasive, whitening inorganic fillermaterial, and the (iv) aqueous medium are based on the total weight ofthe aqueous composition.

The present invention solves problems noted above with the use of (i)porous particles that can scatter visible light, in the cladding(coating) composition for the core of the yarn thereby increasing theopacity of the coating and controlling glare from final coated yarn andwoven textile product. This feature is enhanced by the (i) porousparticles and the presence of an (iii) inorganic filler material asdescribed below. Additionally, this invention provides an aqueouscomposition that can be used as the cladding or coating to preparecoated yarns, using a water-based binder material that provides improvedenvironmental safety and other features over the solvent-basedconventional plastisol coatings currently used in the industry.

DETAILED DESCRIPTION OF THE INVENTION

The following discussion is directed to various embodiments of thepresent invention and while some embodiments can be desirable forspecific uses, the disclosed embodiments should not be interpreted orotherwise considered be limit the scope of the present invention, asclaimed below. In addition, one skilled in the art will understand thatthe following disclosure has broader application than is explicitlydescribed for any specific embodiment.

Definitions

As used herein to define various components of the foamed aqueouscomposition and foamable aqueous composition, substrate materials, ormaterials used to prepare the porous particles, unless otherwiseindicated, the singular forms “a,” “an,” and “the” are intended toinclude one or more of the components (that is, including pluralityreferents).

Each term that is not explicitly defined in the present application isto be understood to have a meaning that is commonly accepted by thoseskilled in the art. If the construction of a term would render itmeaningless or essentially meaningless in its context, the termdefinition should be taken from a standard dictionary.

The use of numerical values in the various ranges specified herein,unless otherwise expressly indicated otherwise, are considered to beapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as the values within the ranges.In addition, the disclosure of these ranges is intended as a continuousrange including every value between the minimum and maximum values.

The terms “porous particle” and “(i) porous particles” are used herein,unless otherwise indicated, to refer to porous organic polymericmaterials useful in the yarns, fabrics (substrates), compositions, andcoatings according to the present invention. The porous particlesgenerally comprise a solid continuous polymeric phase having an externalparticle surface and discrete pores dispersed within the continuouspolymeric phase. The continuous polymeric phase also can be chemicallycrosslinked or elastomeric in nature, or both chemically crosslinked andelastomeric in nature.

The continuous polymeric phase of the (i) porous particles generally hasthe same composition throughout that solid phase. That is, thecontinuous polymeric phase is generally uniform in composition includingany components that can be incorporated therein. In addition, ifmixtures of polymers are used in the continuous polymeric phase,generally those mixtures also are uniformly distributed throughout.

As used in this disclosure, the term “isolated from each other” refersto the different (distinct) pores of same or different sizes that areseparated from each other by some portion of the continuous polymericphase and such pores are not interconnected. Thus, “discrete” poresrefer to “individual” or “closed” non-connected pores or voidsdistributed within the continuous polymeric phase.

The terms “first discrete pore” and “second discrete pore” refer todistinct sets of isolated pores in the (i) porous particles. These firstand second discrete pores can refer to distinct individual pores, or inmost embodiments, they refer to distinct sets of pores. Each distinctset of pores includes a plurality of pores, each of which pores isisolated from others pores in the set of pores, and the pores of eachset of pores are isolated from all other pores of the other sets ofpores in the (i) porous particle. Each set of pores can have the samemode average size or both sets can have the same mode average size. Theword “discrete” is also used to define different droplets of the firstand second aqueous phases when they are suspended in the oil (solvent)phase (described below).

The (i) porous particles can include “micro,” “meso,” and “macro”discrete pores, which according to the International Union of Pure andApplied Chemistry, are the classifications recommended for discrete poresizes of less than 2 nm, from 2 nm to 50 nm, and greater than 50 nm,respectively. Thus, while the (i) porous particles can include closeddiscrete pores of all sizes and shapes (that is, closed discrete poresentirely within the continuous polymeric phase) providing a suitablevolume in each discrete pore, macro discrete pores are particularlyuseful. While there can be open macro pores on the surface of the (i)porous particle, such open pores are not desirable and can be presentonly by accident. The size of the (i) porous particles, theirformulation, and manufacturing conditions are the primary controllingfactors for discrete pore size. However, typically the discrete poresindependently have an average size of at least 100 nm and up to andincluding 7,000 nm, or more likely at least 200 nm and up to andincluding 2,000 nm. Whatever the size of the discrete pores, they aregenerally distributed randomly throughout the continuous polymericphase. However, if desired, the discrete pores can be groupedpredominantly in one part (for example, “core” or “shell”) of the (i)porous particles.

“Opacity” is a measured parameter according to the present invention,that characterizes the “hiding power” of an element or the extent towhich the transmission of electromagnetic radiation such as visiblelight, is blocked. In the present invention, the “opacity” of a coatingcan be quantified by first measuring the luminous reflectance (CIE Ytristimulus value) of the coating when coated over both a white and ablack substrate and then calculating the ratio of these reflectancevalues. The higher the value of this ratio, the greater the opacity.

CIELAB L*, a*, and b* values described herein have the known definitionsaccording to CIE 1976 color space or later known versions of color spaceand can be calculated assuming a standard D65 illuminant and knownprocedures. These values can be used to express a color as threenumerical color values: L* for the lightness (or brightness) of thecolor, a* for the green-red component of the color, and b* for theblue-yellow component of the color values.

Glass transition temperatures of the organic polymers used to preparethe continuous polymeric phase, or (ii) film-forming binder materialsdescribed below, can be measured using Differential Scanning Calorimetry(DSC) using known procedures. For many commercially available organicpolymers, the glass transition temperatures are known from suppliers.

“Openness” (Openness Factor, or OF) refers to how tight the weave is ina fabric material, the percentage of holes in a fabric construction, andis sometimes referred to as “weave density.” The lower the OF, the lessthe light transmittance and the greater the visible light that isobstructed or blocked. OF is the ratio between transparent and opaquesurfaces and depends on the spacing and dimension of the yarn.

As used herein, a “yarn” is a continuous length of interlocked fiberstrands. Yarns are classified according to their structure into threebasic categories: staple fiber yarns are made of several short staplefibers that are wound together; ply yarns are made of one or morestrands of staple fiber yarns; a single ply yarn is a single strand ofstaple fibers held together by twisting. Multi-ply yarns are made ofmultiple single yarns twisted together. Filament yarn is made of one ormore continuous strands that run the entire length of the yarn and arelonger than staple fibers. Multiple filaments can be woven together orintertwined in a suitable manner or arranged together as a bundle withor without intertwining.

As used herein. a “coated yarn” according to the present invention is ayarn that acts as a “yarn core” on which a coating is disposed asdescribed in detail below.

As used herein, the terms “fabric,” “textile,” and “fabric substrate”are meant to refer to materials that are composed of or prepared fromthe coated yarn according to the present invention, of any desirablediameter or length.

Uses

The coated yarns, fabric substrates, and compositions according to thisinvention can be used to prepare or used in various textiles includingthose having heat or other radiation blocking properties. For example,the coated yarns can be used to prepare textiles that block heat (nearinfrared radiation). Alternatively, such textiles can be used assubstrate upon which other materials can be disposed for variouspurposes. Resulting articles can be used as, for example, curtains andother window treatments, carpets, window blinds, room dividers, cubiclecurtains, banners, labels, projection screens, clothing, coverings andtarpaulins (for example for vehicles, boats, and other objects), andpackaging materials. Articles containing the textiles can optionallyhave a printable outer surface able to accept ink used in screenprinting, gravure printing, inkjet printing, thermal imaging (such as“dye sublimation thermal transfer”), or other imaging processes.

Other potential uses of the coated yarns and fabric substrates accordingto the present invention include but are not limited to, mattress andpillow ticking, bedspreads, mattress covers, draperies, awnings,upholstery, automotive and airplane seat covering, protective apparel,wallpaper, flooring materials, and field shelter (tents) materials.

Coated Yarns

Coated yarns designed according to the present invention typicallycomprise a continuous length of yarn forming a yarn core as describedabove. Particularly useful yarn cores comprise a set of one (mono-) ormore (multi-) individual continuous filaments composed of synthetic ornaturally-occurring materials, extending essentially in the samedirection longitudinally. Multifilament yarn cores comprising two ormore individual continuous filaments are useful in many embodiments.

Each coated yarn according to the present invention generally has a meandiameter of at least 25 μm and up to and including 1500 μm or of atleast 100 μm and up to and including 1000 μm. The “mean diameter” is thearithmetic mean of multiple diameter measurements taken of the coatedyarn, for example ten such measurements, using an MSD 25 diametermeasuring device (for example, available from Zumbach). A mono- ormultifilament yarn core can have a denier of at least 75 and up to andincluding 2500 wherein a denier refers to a 1.2 g per 9000 meters of acontinuous strand.

For example, the mono- or multifilament yarn core can have a continuousfilament count of at least 20 and up to including 1000, or more likelyat least 30 and up to and including 500. It is desirable that suchcontinuous filaments be composed of one or more materials that burnpoorly and have a melting point greater than the temperature at whichpolymers coated axially thereon are processed or dried. In someembodiments, each continuous filament can be composed of organic orinorganic materials lacking halogen atoms and are recyclable. Thecontinuous filaments can be of uniform or variable length. Suchmaterials can include but are not limited to, thermoplastic polymerssuch as polyamides (such as nylon); aramids (aromatic polyamides such asNomex); polyesters [such as polyethylene terephthalate (PET)];polyurethanes; polyolefins (such as polypropylenes, polyethylenes, andethylene-propylene copolymers); vinyl polymers (such as vinyl acetateand acrylic resins); cellulosic polymers (such as cellulose acetate);cotton; and glasses (in the form of fiberglass). In addition, eachcontinuous filament can be a mixture of such polymeric materials; and,it is possible for the core to be composed of filaments composed ofdifferent polymeric materials. The fiberglass filaments are particularlyuseful to form a mono- or multifilament core.

The yarn core according to the present invention comprises at least onan average 15 weight % and up to and including 50 weight %, based on thetotal dry weight of the coated yarn. The mean diameter of the yarn coreis generally at least 20 μm and up to and including 1450 μm or of atleast 90 μm and up to and including 950 μm. The “mean diameter” is thearithmetic mean of multiple diameter measurements taken of the yarncore, for example ten such measurements, using an MSD 25 diametermeasuring device (for example, available from Zumbach). The variouscontinuous filaments can be designed with a particular composition, meandiameter, and length to provide a desired tensile strength.

Some or all continuous filaments in the mono- or multifilament yarn corecan comprise one or more additives including but not limited to filament(or fiber) reinforcing materials, polymer stabilizers, UV absorbers,flame retardants, plasticizers, tinting colorants, opacifying colorants,or other materials that one skilled in the art would readily understandas useful in such materials, for example as described in EP 0 900 294B1(noted above).

Each mono- or multifilament yarn core can be prepared using knowntechnology, for example as described in U.S. Patent ApplicationPublication 2007/0015426 (Ahmed et al.), the disclosure of which isincorporated herein by reference.

According to the present invention, a “coating” is disposed coaxially on(or around the entire circumference) of the yarn core, which coating isdescribed in more detail below. In some embodiments, this coating isdisposed coaxially and directly on the yarn core, meaning that there areno intermediate layers, coatings, or disposed materials between thecoating containing (i) through (iii) described below, and the yarn core.In addition, the coating can be the outermost coaxial coating in thecoated yarn. The coating thus provides a generally circular (orco-axial) shape to the coated yarn and can be present at a coverage ofat least 5 g/m² and up to and including 200 g/m².

It is also desirable that the (i) porous particles (described below) arepresent in the coatings at a coverage of at least 4 g/m², or theycomprise at least 2 weight % and up to and including 40 weight %, basedon the total coating weight.

However, in other embodiments, there can be at least one intermediatecoaxial coating, sheath, or zone disposed between the yarn core and thecoating containing the (i) through (iii) components. For example, one ormore intermediate coaxial coatings can be composed of the same ordifferent polymers (such as a flame-retarding polymer), and the same ordifferent types of amounts of non-polymeric flame retardants. Suchcoaxial layer arrangements of intermediate coaxial coatings (or sheaths)are illustrated in FIG. 1 and Columns 4-7 of U.S. Pat. No. 9,920,458(noted above), the disclosure of which is incorporated herein byreference. It is desirable that the one or more intermediate coaxialcoatings be detectably different in some manner (for example, chemicalcomposition, optical properties, or other properties) from the coatingcontaining (i) through (iii) components described below. In suchembodiments, the coating described herein containing the (i) through(iii) components is disposed coaxially on the outermost intermediatecoaxial coating and is also generally the outermost coaxial coating inthe coated yarn. One or more intermediate coaxial coatings can bedesigned to be present at a coating weight that would be readilyapparent to one skilled in the art. Any or all intermediate coaxialcoatings can include one or more flame retardants, plasticizers, tintingagents, or other additives that would be readily apparent to one skilledin the art.

In most useful embodiments, the “coating” described herein as disposedon the yarn core can be an “aqueous-based coating” derived from anaqueous composition as described in more detail below.

The coatings disposed on the yarn core according to the presentinvention comprises three essential components: (i) porous particles,(ii) one or more film-forming binders; and (iii) an inorganic fillermaterial, all of which are described below in more detail. In manyembodiments, such coatings “consist essentially of” the noted (i), (ii),and (iii) components as these components are the only one essential toproviding the inventive properties described above.

The respective amounts of these essential components are based on thetotal weight of the coating disposed on the yarn core, including anyresidual (iv) solvent medium (described below). The (i) porous particlescan be present in an amount of at least 4 weight % and up to andincluding 20 weight %, or at least 7 weight % and up to and including 15weight %. The (ii) film-forming binder material (or mixtures thereof)can be present in an amount of at least 40 weight % and up to andincluding 90 weight %, or of at least 50 weight % and up to andincluding 80 weight %. Moreover, the, (iii) inorganic filler material(or mixtures thereof) can be present in an amount of at least 4 weight %and up to and including 30 weight %, or in an amount of at least 7weight % and up to and including 20 weight %.

It is also desirable in some embodiments that the weight ratio of the(ii) film-forming binder material to the (i) porous particles in thecoating is at least 2:1 to and including 25:1; the weight ratio of the(ii) film-forming binder material to the (iii) inorganic filler materialin the coating is at least 1.5:1 to and including 25:1; or the weightratio of the (i) porous particles to the (iii) inorganic filler materialin the coating is at least 0.1:1 to and including 5:1. Two or all threeof these weight ratio conditions can be present simultaneously ifdesired.

(i) Porous Particles

Each of the (i) porous particles useful in the coating comprises acontinuous polymeric phase and discrete pores distributed within thecontinuous phase and has a mode particle size of at least 2 μm and up toand including 50 μm. The (i) porous particles can be prepared using oneor more water-in-oil emulsions in combination with an aqueous suspensionprocess, such as in the Evaporative Limited Coalescence (ELC) process.The details for the preparation of the porous particles are provided,for example, in U.S. Pat. No. 8,110,628 (Nair et al.), U.S. Pat. No.8,703,834 (Nair), U.S. Pat. No. 7,754,409 (Nair et al.), U.S. Pat. No.7,887,984 (Nair et al.), U.S. Pat. No. 8,329,783 (Nair et al.), and U.S.Pat. No. 8,252,414 (Putnam et al.), the disclosures of all of which areincorporated herein by reference. Thus, the (i) porous particles aregenerally polymeric and organic in nature (that is, the continuouspolymeric phase is polymeric and organic in nature) and non-porousparticles (having less than 20 volume % porosity) are generally excludedfor use in the present invention. Smaller inorganic particles can bepresent on the outer surface of the (i) porous particles as noted below.It is desirable that the porous particles contain no opacifyingcolorants such as carbon black.

The (i) porous particles generally have a porosity of at least 20 volume% and up to and including 70 volume %, or at least 35 volume % and up toand including 65 volume %, or more typically at least 40 volume % and upto and including 60 volume %, all based on the total porous particlevolume. Porosity can be measured using the known mercury intrusiontechnique.

The (i) porous particles can be composed of a continuous polymeric phasederived from one or more organic polymers that are chosen so that thecontinuous polymeric phase has a glass transition temperature (T_(g)) ofat least 25° C., or more typically of at least 25° C. and up to andincluding 180° C., as determined using Differential ScanningCalorimetry.

The continuous polymeric phase can comprise one or more organic polymershaving the properties noted above and comprise generally at least 70weight % and up to and including 100 weight % based on the total weightof the continuous polymeric phase. In some embodiments, the continuouspolymeric phase is composed of one or more cellulose polymers (orcellulosic polymers) including but not limited to, those cellulosicpolymers derived from one or more of cellulose acetate, cellulosebutyrate, cellulose acetate butyrate, and cellulose acetate propionate.Mixtures of these cellulose polymers can also be used if desired, andmixtures comprising a polymer derived from cellulose acetate butyrate asat least 80 weight % of the total of cellulose polymers (or of allpolymers in the continuous polymeric phase) are particularly useful.Details about such polymers are provided, for example, in U.S. Pat. No.9,963,569 (Nair et al.), the disclosure of which is incorporated hereinby reference

In other embodiments, the continuous polymeric phase can comprise one ormore organic polymers such as polyesters, styrenic polymers (for examplepolystyrene and polychlorostyrene), mono-olefin polymers (for example,polymers formed from one or more of ethylene, propylene, butylene, andisoprene), vinyl ester polymers (for example, polymer formed from one ormore of vinyl acetate, vinyl propionate, vinyl benzoate, and vinylbutyrate), polymers formed from one or more α-methylene aliphaticmonocarboxylic acid esters (for example, polymers formed from one ormore of methyl acrylate, ethyl acrylate, butyl acrylate, dodecylacrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethylmethacrylate, butyl methacrylate, and dodecyl methacrylate), vinyl etherpolymers (such as polymers formed from one or more of vinyl methylether, vinyl ethyl ether, and vinyl butyl ether), and vinyl ketonepolymers (for example, polymers formed from one or more of vinyl methylketone, vinyl hexyl ketone, and vinyl isopropenyl ketone). Other usefulpolymers include polyurethanes, urethane acrylic copolymers, epoxyresins, silicone resins, polyamide resins, and polyesters of aromatic oraliphatic polycarboxylic acids with one or more aliphatic diols, such aspolyesters of isophthalic or terephthalic or fumaric acid with diolssuch as ethylene glycol, cyclohexane dimethanol, and bisphenol adductsof ethylene or propylene oxides. The polyesters can be saturated orunsaturated. Other useful polyesters include lactic acid polymers,glycolic acid polymers, caprolactone polymers, and hydroxybutyric acidpolymers. Details of such useful polymers are provided, for example inU.S. Pat. No. 9,891,350 (Lofftus et al.) and U.S. Pat. No. 9,469,738(Nair et al.), the disclosures of both of which are incorporated hereinby reference. Mixtures of one or more of such polymers with one or moreof the cellulose polymers described above can also be used.

The continuous polymeric binder of the (i) porous particles can also bederived from ethylenically unsaturated polymerizable monomers andpolyfunctional reactive compounds as described for example in U.S. Pat.No. 8,703,834 (Nair et al.), the disclosure of which is incorporatedherein by reference.

In general, the (i) porous particles used in the present invention havea mode particle size equal to or less than 50 μm, or of at least 2 μmand up to and including 50 μm, or typically of at least 3 μm and up toand including 30 μm or even up to and including 40 μm. Most useful (i)porous particles have a mode particle size of at least 3 μm and up toand including 20 μm. Mode particle size represents the most frequentlyoccurring diameter for spherical particles and the most frequentlyoccurring largest diameter for the non-spherical particles in a particlesize distribution histogram, which can be determined using knownequipment (including light scattering equipment such as the Sysmex FPIA3000 Flow Particle Image Analyzer that used image analysis measurementsand that can be obtained from various sources including MalvernPanalytical; and coulter counters and other particle characterizingequipment available from Beckman Coulter Diagnostics), software, andprocedures.

Pore stabilizing materials such as hydrocolloids can be present withinat least part of the volume of the discrete pores distributed throughoutthe continuous polymeric phase, which pore stabilizing materials aredescribed in the Nair, Nair et al., and Putnam et al. patents citedabove. For example, the pore stabilizing material can be selected fromthe group consisting of carboxymethyl cellulose (CMC), a gelatin, aprotein or protein derivative, polyvinyl alcohol and its derivatives, ahydrophilic synthetic polymer, and a water-soluble microgel.

It can be desirable in some embodiments to provide additional stabilityof one or more discrete pores in the (i) porous particles during theirformation, by having one or more amphiphilic block copolymers disposedat the interface of the one or more discrete pores and the continuouspolymeric phase. Such materials are “low HLB”, meaning that they have anHLB (hydrophilic-lipophilic balance) value as it is calculated usingknown science, of 6 or less, or even 5 or less. The details of theseamphiphilic polymers and their use in the preparation of the (i) porousparticles are provided in U.S. Pat. No. 9,029,431 (Nair et al.), thedisclosure of which is incorporated herein by reference. A particularlyuseful amphiphilic block copolymer useful in such embodiments comprisespoly(ethyleneoxide) and poly(caprolactone) that can be represented asPEO-b-PCL. Amphiphilic block copolymers, graft copolymers and randomgraft copolymers containing similar components are also useful includingother polymeric emulsifiers such as GRINDSTED® PGPR 90, polyglycerolpolyricinolate emulsifier, obtained from Danisco, Dupont.

The (i) porous particles used in this invention can be spherical ornon-spherical depending upon the desired use. In a method used toprepare the (i) porous particles, additives (shape control agents) canbe incorporated into the first or second aqueous phases, or in the oil(organic) phase to modify the shape, aspect ratio, or morphology of the(i) porous particles. The shape control agents can be added prior to orafter forming the water-in-oil-in-water emulsion. In either case, theinterface at the oil and second water phase is modified before organicsolvent is removed, resulting in a reduction in sphericity of the porousparticles. The (i) porous particles used in the present invention canalso comprise surface stabilizing agents, such as colloidal silica, onthe outer surface of each porous particle, in an amount of at least 0.1weight %, based on the total dry weight of the (i) porous particle.

The average size of the discrete pores in the (i) porous particles isdescribed above.

The (i) porous particles can be provided as powders, or as aqueoussuspensions (including water or water with water-miscible organicsolvents such as alcohols). Such powders and aqueous suspensions canalso include surfactants or suspending agents to keep the (i) porousparticles suspended or to facilitate rewetting them in an aqueousmedium.

In a dry coating disposed on the mono- or multifilament core, the largemismatch in refractive index between the discrete pores of the (i)porous particles and the polymer walls (continuous polymeric phase),causes incident electromagnetic radiation passing through theaqueous-based coating to be scattered by the multiplicity of interfacesand discrete pores. The back scattered electromagnetic radiation canagain be scattered and returned in the direction of the incidentelectromagnetic radiation thus reducing the attenuation and contributingto the opacifying power and lightness or luminous reflectance of theaqueous-based coating.

(ii) Film-Forming Binder Materials

The one or more (ii) film-forming binder materials present in thecoatings are designed so that they have the following properties: theyare generally water-soluble or water-dispersible; they are capable ofbeing disposed onto a suitable yarn core as described below; they arecapable of being dried and where desired also crosslinked (or at leastpartially cured); they have good light and heat stability; and they arefilm-forming but contribute to the flexibility of the coated yarn andare thus not too brittle, for example having a T_(g) of less than 25°C., a T_(g) of less than or equal to 0° C., a T_(g) of less than orequal to −10° C., or less than or equal to −25° C., all as determinedusing Differential Scanning Calorimetry.

The (ii) film-forming binder materials can include one or more organicpolymers that are film forming and that can be provided as an emulsion,dispersion, or in an aqueous solution. They can also include polymersthat are self-crosslinking, or it can include one or more polymers thatare self-crosslinking or self-curable, or they can include one or morepolymers to which crosslinking agents are added and are thus curable orcapable of being at least partially crosslinked or cured underappropriate conditions.

Thus, if a (ii) film-forming binder material is crosslinkable (orcurable) in the presence of a suitable crosslinking agent or catalyst,such crosslinking (or curing) can be activated chemically with heat,radiation, or other known means. A curing or crosslinking process servesto provide improved insolubility of the resulting coated layer as wellas cohesive strength and adhesion to the coated yarn core. The curing orcrosslinking agent is generally a chemical having functional groupscapable of reacting with reactive sites in a (ii) film-forming bindermaterial (such as a functionalized latex polymer) under curingconditions to thereby produce a crosslinked structure. Representativecrosslinking agents include but are not limited to, multi-functionalaziridines, aldehydes, methylol derivatives, and epoxides.

Useful (ii) film-forming binder materials include but are not limited,to water-soluble or water-dispersible polymers of the following types:poly(vinyl alcohol), poly(vinyl pyrrolidone), ethylene oxide polymers,polyurethanes, urethane-acrylic copolymers, other acrylic polymers,styrene-acrylic copolymers, vinyl polymers, vinyl acrylic copolymers,styrene-butadiene copolymers, acrylonitrile copolymers, and polyesters,silicone polymers or a combination of two or more of these organicpolymers. Such (ii) film-forming binder materials, such as acrylicpolymers, are readily available from various commercial sources or canbe prepared using known starting materials and synthetic conditions. Auseful class of (ii) film-forming binder materials includes aqueouslatex polymer dispersions such as acrylic latexes that can be ionic ornonionic colloidal dispersions of acrylate polymers and copolymers.Useful film-forming aqueous latexes include styrene-butadiene latexes,poly(vinyl chloride) and poly(vinylidene chloride) latexes, poly(vinylpyridine) latexes, poly(acrylonitrile) latexes, and latexes formed fromacrylonitrile, butyl acrylate, and ethyl acrylate. A useful mixture of(ii) film-forming binder materials includes but is not limited to, amixture of poly(vinyl chloride) and a non-halogenated acrylic polymer,in suitable weight ratios, or copolymers derived from vinyl chloride andone or more non-halogenated acrylic monomers.

(iii) Inorganic Fillers Materials

Useful (iii) inorganic filler materials in the coating according to thisinvention are desirably those that can impart lightness (or brightness)and opacity to the coating and have a MOHS scale of mineral hardnessvalue of less than 5 and generally at least 1 and up to and including 5,or even at least 2 and up to and including 4.5. Such hardness valuesensure that inorganic fillers are minimally abrasive to the yarn coressuch as for example multifilament fiberglass yarn cores and do notabrade the die used in manufacturing for depositing the coating as asheath around the yarn core. Thus, such inorganic filler materials canalso be considered “non-abrasive, whitening inorganic filler materials”.

Examples of useful inorganic filler materials include but are notlimited to, zinc sulfide, barium sulfate, calcium carbonate, mica,fluorite, clay, and gypsum. Mixtures of different organic fillermaterials can be used if desired, such as a mixture of zinc sulfide(MOHS value of 3.8) and barium sulfate (MOHS value of 3-3.5), insuitable weight ratios. The MOHS scale of hardness is known as aquantitative measure of scratch resistance and the relative hardness ofone material compared to another. This value can be determined by, forexample, by using a sclerometer, or by using comparisons with materialsof known MOHS values. The MOHS scale of hardness value for some usefulmaterials is known in the literature.

Optional Materials:

While the (i) porous particles, (ii) film-forming binder materials, and(iii) inorganic fillers described above are the only essential materialsused in the coating necessary to achieve the inventive propertiesdescribed above, some optional materials may be included as long as theydo not materially interfere with those inventive properties. Suchoptional materials can be present in a total amount of less than 30weight %, based on the total weight of the coating. Such optionalmaterials can include but are not limited to, thickening agents, flameretardants, UV radiation stabilizers, heat stabilizers, tinting agents,dispersants, biocides, lubricants, and moisture or deflection controlagents, individually or in any combination.

These optional materials can be incorporated into the coating in anysuitable location that is technically practical, such as within the (i)porous particles (either within discrete pores, the continuous polymericphase, or in both the discrete pores and continuous polymeric phase);within the (ii) film-forming binder materials; or with both (i) porousparticles and (ii) film-forming binder materials. Various optionalmaterials can be in different locations in the coating.

Useful thickening agents can be present to modify the viscosity of thecomposition (coating formulation) before it is applied to the mono- ormultifilament core yarn. Particularly useful rheology modifiers areRHEOLATE® HX 6010 (Elementis), OPTIFLO®-T 1000 (BYK), RHEOVIS® PU 1214(BASF), ACRYSOL® G111 (Dow Chemical Company), and PARAGUM products(Royal Adhesives, Inc.).

Useful flame retardants can be present to reduce the flammability of theyarn strands and can include but are not limited to, phosphorus- ornitrogen-containing flame retardants such as ammonium polyphosphates;melamine isocyanurate; derivatives or pentaerythritol and a melamine;and ammonium molybdates. More specific examples of useful compounds areprovided in [0036]-[0043] of U.S. Patent Application Publication2013/0052900 (Jung et al.), the disclosure of which is incorporatedherein by reference.

Tinting agents can be present to provide a specific observable color,coloration, or hue in the resulting continuous yarn strand andsubstrates. Mixtures of tinting colorants can be present, and they canbe different in composition and amounts. The desired coloration or huecan be obtained using specific tinting colorants can be used incombination with specific amounts of (i) porous particles to offset ormodify the original color of a continuous yarn strand to provide morewhiteness (or brightness) in the final “color” (or coloration). The oneor more tinting colorants can be incorporated within the (i) porousparticles (either within the volume of discrete pores, within thecontinuous polymeric phase, or in both places) or they can be uniformlydispersed within the (ii) film-forming binder material. Alternatively,one or more tinting colorants can be present within both the (i) porousparticles (in a suitable location) and within the (ii) film-formingbinder material. The one or more tinting colorants can be present in anamount of at least 0.0001 weight %, or more typically at least 0.001weight %, and up to and including 3 weight %, based on the total weightof the coating. Tinting colorants can be dyes or organic pigments thatare soluble or dispersible in organic solvents and polymers that areused for making the (i) porous particles and thus can be included withinthe oil phase used to prepare such (i) porous particles. Alternatively,the tinting colorants can be primarily water-soluble orwater-dispersible materials that are included into an aqueous phase usedto prepare the (i) porous particles.

Dispersants can be present in the water-based coating to providecolloidal stability and prevent agglomeration of the solid particlesthereby ensuring storage stability (no viscosity instability, noseparation) in the aqueous formulation Examples of useful dispersantsinclude but are not limited to, TERGITOL® ethoxylated alcohols andwater-dispersible and water-soluble SOLSPERSE® 43000 polymericdispersants.

Biocides (that is, antimicrobial agents or antifungal agents) can bepresent to reduce or prevent growth of microorganisms and fungi in thecontinuous yarn strands and substrate prepared therefrom. Such materialscan include but are not limited to, silver metal (for example, silverparticles, platelets, or fibrous strands) and silver-containingcompounds such as silver chelates and silver salts such as silversulfate, silver nitrate, silver chloride, silver bromide, silver iodide,silver iodate, silver bromate, silver tungstate, silver phosphate, andsilver carboxylates. In addition, copper metal (for example, copperparticles, platelets, or fibrous strands) and copper-containingcompounds such as copper chelates and copper salts can be present as (c)additives for biocidal purposes. Mixtures of any of silver metal,silver-containing compounds, copper metal, and copper-containingcompounds, can also be present and used in this manner.

After application and drying, the coating generally has very little (iv)aqueous medium (such as water) left from the original composition (or“coating formulation”). That is, the residual amount of (iv) aqueousmedium can be as little as 5 weight % or less, or even 1 weight % orless, based on the total weight of the coating.

Aqueous Compositions (or Coating Formulations)

The coating used according to the present invention is provided byapplication to the yarn core (such as a mono- or multifilament core) ofan aqueous composition that comprises (or consists essentially of) the(i) porous particles described above, (ii) a film-forming bindermaterial as described above, (iii) an inorganic filler material asdescribed above, and (iv) an aqueous medium.

In general, the (iv) aqueous medium is designed so that the (ii)film-forming polymers described above are soluble or dispersibletherein. Thus, it is highly desirable that the (iv) aqueous medium havepredominantly water as the solvent. For example, the (iv) aqueous mediumcan comprise water in an amount of at least 80 weight %, at least 95weight %, or even 100 weight %, based on the total solvents therein. The(iv) aqueous medium can contain very low amounts of auxiliary solventsother than water, and if they are present, they are generallywater-miscible in nature and include but are not limited to alcohols andacetone. Such auxiliary solvents do not adversely affect formulation oruse of the aqueous-based composition.

The (iv) aqueous medium can comprise at least 35 weight % and up to andincluding 70 weight %, or typically at least 40 weight % and up to andincluding 60 weight %, of the total weight of the composition (orcoating formulation).

The solids content in the aqueous compositions according to the presentinvention is generally at least 30% and up to and including 65%, or atleast 35% and up to and including 55%.

The amounts of the essential components (i) porous particles, (ii)film-forming binder materials, and (iii) inorganic filler materials, areas follows, all amounts being based on the total weight of the aqueouscomposition:

The (i) porous particles are generally present in the aqueouscompositions in an amount of at least 2 weight % and up to and including10 weight %, or typically at least 4 weight % and up to and including 8weight %, based on the total weight of the composition [including (iv)solvent medium], particularly when the (a) porous particles have a modesize of at least 3 μm and up to and including 30 μm.

The one or more (ii) film-forming binder materials can be present in anamount of at least 25 weight % and up to and including 60 weight %, ortypically at least 30 weight % and up to and including 50 weight %.

The (iii) inorganic filler material (or mixture thereof) such asnon-abrasive, whitening inorganic filler materials, can be present in anamount of at least 2 weight % and up to and including 15 weight %.

The aqueous compositions according to the present invention to form thecoating on the mono- or multifilament core generally has a viscosity ofat least 5 centipoise (0.005 Pa-sec) and up to and including 5000centipoise (5 Pa-sec) as measured at a shear rate of 10K sec⁻¹ and 25°C. using known procedures and equipment.

The compositions according to the present invention can be prepared bymixing the components using suitable mixers such as an overhead stirrerattached with a Cowles blade, impeller or turbine blade in order tobreak up agglomerated particles and create a stable suspension of finesolids.

Fabric Substrates

Continuous yarns can be prepared using suitable extrusion techniquesknown in the art. In the practice of the present invention, the coatedyarn is readily prepared by passing the yarn core (such as a mono- ormultifilament core) through a bath comprising the aqueous coatingcomposition and then through a heat treatment that serves to remove thewater and any other solvents, and to cure or set the film-forming bindermaterial. Application of the aqueous composition can be achieved byconventional immersion, contact or spray methods using rollers, pads,apron applicators, sprays, or jets, or a combination thereof. Aparticularly useful method to form the coating in a coaxial mannerincludes withdrawing the yarn core from a supply bobbin and passing itthrough a receptacle wherein it is immersed in the aqueous compositionaccording to the present invention; then passing the coated yarn corethrough a die that serves to remove excess aqueous composition; followedby treating the coated yarn core in an oven maintained at a temperatureadequate to dry the aqueous composition and to cure the film-formingbinder material; and then the resulting coated yarn is wound onto a takeup reel.

The fabric substrates according to the present invention can be preparedby appropriate weaving or other manufacturing process using a pluralityof coated yarns according to this invention. For example, the coatedyarn can be subjected to warping, weaving, tentering, and packagingoperations to obtain a fabric substrate and formed into a fabricsubstrate of any size or shape. Alternatively, the coated yarn can bewoven, interlocked, spun, knitted, or adhesively-bonded using techniquesknown in the art. The coated yarn strands can vary in dry thickness andlength as long as they are suitable for the fabric substrate and itsintended purpose. In most embodiments, the fabric substrate thickness isat least 50 μm. The coated yarn should have suitable hardness, tensilestrength, lot moisture content (for example, less than 1 weight % at 70%relative humidity), elongation, and light fastness. Details about suchprocesses are provided in [0072] through of U.S. Patent ApplicationPublication 2013/0052900 (Jung et al.), the disclosure of which isincorporated herein by reference.

The fabric substrates prepared according to the present inventiongenerally have an openness (or Openness Factor) of 0% and up to andincluding 15%, or at least 1% and up to and including 10%, or morelikely at least 3% and up to and including 10%.

As noted above, the fabric substrates can be used in many ways, and theycan be used “as is” or they can be subjected to further operations toincorporate them into various articles and devices. For example, thefabric substrates can be coated with other materials for variouspurposes, and they can be laminated to films, papers, or other elements.

It is further possible to print images on an outer surface of a fabricsubstrate using any suitable printing means such as inkjet printing orflexographic printing, thereby forming printed images of text, pictures,symbols, or combinations thereof. Such printed images can be visible, orthey can invisible to the unaided eye (for example, using fluorescentdyes in the printed images). Alternatively, an outer surface can becovered by suitable means with a colorless layer to provide a desiredprotective finish.

A thermally printed image can be formed on either outer surface, forexample, by using a thermal (sublimable) dye transfer printing process(using heat and with or without pressure) from one or more thermal donorelements comprising a dye donor layer comprising one or more dyesublimation printable colorants. For example, a thermal colorant imagecan be obtained using one or more thermal dye patches with or without athermal colorless (clear) patch. Useful details of such a process tomake thermally printed images are provided in copending and commonlyassigned U.S. Ser. No. 15/590,342 (filed May 9, 2017 by Nair andHerrick), the disclosure of which is incorporated herein by reference.

The present invention provides at least the following embodiments andcombinations thereof, but other combinations of features are consideredto be within the present invention as a skilled artisan would appreciatefrom the teaching of this disclosure:

1. An aqueous composition comprising:

(i) porous particles present in an amount of at least 2 weight % and upto and including 10 weight %, each porous particle comprising acontinuous polymeric phase and discrete pores dispersed within thecontinuous polymeric phase, the porous particles having a mode particlesize of at least 2 μm and up to and including 50 μm;

(ii) a film-forming binder material having a T_(g) of less than or equalto 25° C., which film-forming binder material is present in an amount ofat least 25 weight % and up to and including 60 weight %;

(iii) an inorganic filler material having a value of less than 5 on theMOHS scale of mineral hardness, which non-abrasive, whitening inorganicfiller material is present in an amount of at least 2 weight % and up toand including 15 weight %; and

(iv) an aqueous medium in an amount of at least 35 weight % in which thefilm-forming binder material is soluble or dispersible,

wherein the amounts of the (i) porous particles, the (ii) film-formingbinder material, the (iii) inorganic filler material, and the (iv)aqueous medium are based on the total weight of the aqueous composition.

2. The aqueous composition of embodiment 1, consisting essentially ofthe (i) porous particles, the (ii) film-forming binder material, the(iii) inorganic filler material, and the (iv) aqueous medium.

3. The aqueous composition of embodiment 1 or 2, wherein the (iv)aqueous medium comprises water in an amount of at least 80 weight %,based on the total weight of solvents.

4. The aqueous composition of any of embodiments 1 to 3 having aviscosity of at least 5 centipoise (0.005 Pa-sec) and up to andincluding 5000 centipoise (5 Pa-sec) at a shear rate of 10K sec⁻¹ asmeasured at 25° C.

5. The aqueous composition of any of embodiments 1 to 4, wherein the(iii) inorganic filler material is a non-abrasive, whitening inorganicfiller material.

6. The aqueous composition of any of embodiments 1 to 5, wherein the(iii) inorganic filler material comprises barium sulfate, calciumcarbonate, mica, fluorite, clay, gypsum, or zinc sulfide.

7. The aqueous composition of any of embodiments 1 to 6, wherein the(iii) inorganic filler material comprises zinc sulfide.

8. The aqueous composition of any of embodiments 1 to 7, wherein the (i)porous particles have a mode particle size of at least 3 μm and up toand including 30 μm, a porosity of at least 30 volume % and up to andincluding 65 volume %, and have a continuous polymeric phase composed ofone or more of a polyester, a vinyl copolymer, and a cellulosic polymersuch as cellulose acetate, cellulose butyrate, cellulose acetatebutyrate, and cellulose acetate propionate.

9. The aqueous composition of any of embodiments 1 to 8, having a solidscontent of at least 30% and up to and including 65%.

10. The aqueous composition of any of embodiments 1 to 9, wherein the(ii) film-forming binder material comprises one or more acrylicpolymers.

11. The aqueous composition of any of embodiments 1 to 10, wherein the(ii) film-forming binder material comprises a copolymer derived fromvinyl chloride and one or more non-halogenated acrylic monomers.

12. The aqueous composition of any of embodiments 1 to 11, furthercontaining one or more of the following optional materials that aredifferent from all of (i), (ii), and (iii): thickening agent, flameretardant, UV radiation stabilizer, tinting agent, dispersant, biocide,heat stabilizer, lubricant, and moisture or deflection control agent,and the total amount of all of these optional materials is less than 15weight %, based on the total weight of the aqueous composition.

13. The aqueous composition of any of embodiments 1 to 12, wherein the(i) porous particles contain no carbon black.

The following Examples are provided to illustrate the practice of thisinvention and are not meant to be limiting in any manner. The followingmaterials were used in the Examples.

Materials Used in the Following Examples

The continuous polymeric phase polymers used in the following exampleswere the Eastman™ Cellulose Acetate Butyrate 381-0.5 (CAB), a celluloseester, T_(g) of 130° C. (obtained from Chem Point).

NALCO® 1060 containing colloidal silica was obtained from Nalco ChemicalCompany as a 50 weight % aqueous dispersion.

The poly(methylamino ethanol adipate) (AMAE) co-stabilizer was preparedusing known procedures and starting materials.

Carboxy methylcellulose (CMC, 250,000 kDa) was obtained from AcrosOrganics or from Ashland Aqualon as Aqualon 9M31F. These products wereused interchangeably.

The amphiphilic block copolymer of polyethylene oxide andpolycaprolactone (PEO-b-PCL) 5K-20K, was prepared using the proceduredescribed in U.S. Pat. No. 5,429,826 (Nair et al.) where the firstnumber is the molecular weight of the hydrophilic block segment, PEO,and the second number is the molecular weight of the oleophilic blocksegment, PCL.

TERGITOL® 15-S-7, a C12-C14 secondary alcohol surfactant having an HLBvalue of 12.4, was obtained from the Dow Chemical Corp.

The optical brightener TINOPAL® OB CO was obtained from BASFCorporation.

VYCAR® 460×46 a PVC-acrylic copolymer emulsion, used as the binderpolymer was obtained from Lubrizol Corp.

TERGITOL® NP-30 surfactant, a nonylphenol ethoxylate surfactant, wasobtained from the Dow Chemical Corp.

SACHTOLITH HD-S Zinc Sulfide was obtained from Venator Corp.

Campine HT antimony trioxide was obtained from Campine Corp.

RHEOLATE® HX 6010 thickener was obtained from Elementis Corp.

Coatings to determine opacity were made on a Leneta card form 2C-opacity(possessing both black and white regions) obtained from Leneta Company.

Yarn 1 was SULKY® 40 wt 100% viscose/rayon multifilament fiber threadhaving a thickness of 0.33 mm.

Yarn 2 was a transparent monofilament fishing line with a thickness of0.37 mm.

Preparation of Porous Particles

The (i) porous particles (P) used in the Invention Example containedcellulose acetate butyrate without any opacifying pigment were preparedas described in U.S. Pat. No. 9,963,569 (noted above). The resulting (i)porous particles had a particle size of 5.5 μm and a porosity of 52.2%.

Measurements

The mode particle size of the (i) porous particles used in the Exampleswas measured using a Sysmex FPIA-3000 automated particle size analyzerfrom Malvern Instruments. The particle size of the dispersed pigmentswas determined using light scattering.

The porosity of the (i) porous particles was measured using a modifiedversion of the known mercury intrusion porosimetry method.

The opacity of each formulation coated on the Leneta card was determinedby first measuring the Y tristimulus values (in the 400-700 nmwavelength range) of the dry coatings over both the black and whiteregions of the card using a Hunter Labs UltraScan XE colorimeter. Thecolorimeter was equipped with an integrating sphere, a pulsed Xenonlight source, and appropriate filters to simulate standard D65illumination. The following equation was used to calculate a numericalvalue for the opacity of each aqueous formulation:

${{Opacity}\mspace{14mu}(\%)} = {\frac{Y_{black}}{Y_{{white}\;}} \times 100}$

In order to measure the lightness of coatings on Yarn 1 and Yarn 2, andthe opacity of the coating on Yarn 2, each sample was wound on smallsquares of black or white corrugated cardboard. The spectral reflectanceand CIE Tristimulus values of each wound sample were then measured inthe 400-700 nm wavelength range using an X-Rite SP-60 portablespectrophotometer equipped with an integrating sphere, a Tungsten lightsource, and appropriate filters to stimulate D65 illumination. A lighttrap and standard white tile were used to fix the percent reflectancerange from 0 to 100%. The measured X, Y, and Z tristimulus values wereused to calculate specific values for the lightness (L*), red-greencharacter (a*), and yellow-blue character (b*) and opacity of eachcoated and uncoated, wound yarn sample. The CIE Y tristimulus value wasused as a measure of the luminous reflectance or lightness of eachsample.

Comparative Example 1

An aqueous composition was prepared by combining 42.1 weight % of VYCAR®460×46 as a (ii) film-forming binder material, 0.05 weight % ofTERGITOL® NP-30 surfactant, 7.0 weight % SACHTOLITH HD-S zinc sulfide asa (iii) non-abrasive, whitening inorganic filler material, 0.6 weight %Campine HT antimony trioxide, and water in a container. The resultingformulation was mixed using a Cowles blade until all particles were welldispersed, then thickened by adding 1 weight % RHEOLATE® HX 6010thickener. The resulting aqueous composition was coated using a bladewith a 0.005 inch (0.13 mm) gap onto Substrate 1 (described above),dried at 120° C., and followed by curing at 160° C. to form a dry layeron a Leneta card for obtaining opacity measurements.

Comparative Example 2

Comparative Example 2 was prepared in the same manner as the ComparativeExample 1, except 5 weight % of (i) porous particles P were used inplace of the zinc sulfide in the aqueous formulation.

Comparative Example 3

Comparative Example 3 was prepared in the same manner as the ComparativeExample 1 except no zinc sulfide or (i) porous particles (P) werepresent in the aqueous formulation.

Invention Example 1

Invention Example 1 was prepared in the same manner as the ComparativeExample 1 except 5.2 weight % of (i) porous particles P were used inplace of an equivalent amount of the VYCAR® 460×46 film-forming bindermaterial.

Comparative Example 4

An aqueous formulation was prepared as in Comparative Example 1 andplaced in a trough where a sample of Yarn 1 (described above) wasimmersed, passed through a 0.7 mm die orifice, dried, and cured at 160°C. to form a coated yarn having the dried coating disposed coaxially onthe multifilament core, which resulting coated yarn was measured forlightness and luminous reflectance as described above.

Comparative Example 5

An aqueous formulation was prepared as in Comparative Example 1 andplaced in a trough where a sample of Yarn 2 (described above) wasimmersed, passed through a 0.7 mm die orifice, dried, and cured at 160°C. to form a coated yarn having the dried coating disposed coaxially onthe multifilament core, which resulting coated yarn was measured forlightness and luminous reflectance as described above.

Invention Example 2

The coated Yarn 1 of Invention Example 2 was prepared in the same manneras the Comparative Example 4 except 5.2 weight % of (i) porous particlesP were used in place of an equivalent amount of the VYCAR® 460×46film-forming binder material.

Invention Example 3

The coated Yarn 2 of Invention Example 3 was prepared in the same manneras the Invention Example 2 except a different yarn was used.

The resulting obtained opacity and colorimetry data for the preparedarticles and yarns and coated yarns are shown in the following TABLES I,II, and III.

TABLE I Coated on Leneta Card Opacity Comparative Example 1 65.49Comparative Example 2 7.83 Comparative Example 3 6.38 Invention Example1 72.51

The data in TABLE I indicate that the aqueous composition according tothe present invention containing zinc sulfide as a (iii) non-abrasive,whitening inorganic filler material and (i) porous particles, coated ona Leneta card for testing opacity of the resulting coatings, InventionExample 1, exhibited higher opacity compared to those coatings preparedin the Comparative Examples 1-3 using zinc sulfide alone as a (iii)inorganic filler material, (i) porous particles P alone, or with bothzinc sulfide and (i) porous particles P absent, in concentrationscomparable to the aqueous composition.

TABLE II Yarn 1 wound over black L* a* b* Y Uncoated 78.22 −2.77 −4.9953.59 Comparative 85.24 −2.84 0.38 66.48 Example 4 Invention 88.88 −1.98−4.21 73.90 Example 2

The data in TABLE II indicate that coated yarns can be prepared bycoating an aqueous composition according to the present inventioncontaining zinc sulfide as a (iii) inorganic filler material and (i)porous particles on a multifilament core, and the resulting coated yarnsexhibited higher L* values compared to the uncoated multifilament core(yarn) and the coated yarns prepared in the Comparative Examples 4. Thecoated yarn prepared according to the present invention also exhibited asignificantly higher degree of lightness as indicated by the Ytristimulus value of luminous reflectance.

TABLE III L* a* b* Y wound over wound over wound over wound over Yarn 2Opacity black black black black Uncoated 19.01 45.99 −0.40 −0.41 15.26Comparative 79.41 85.23 −1.34 0.24 66.46 Example 5 Invention 88.49 90.31−0.50 −2.59 76.98 Example 3

The data in TABLE III similarly indicate that additionally, thetransparent Yarn 2 coated with an aqueous composition containing zincsulfide as a (iii) inorganic filler material and (i) porous particlesInvention Example 3, according to the present invention, was madeopaque. The resulting coated yarn exhibited higher opacity compared tothose prepared in the Comparative Example 5 using zinc sulfide alone.The inventive coated yarn exhibited L* and luminous reflectance valuesthat were greater compared to the uncoated multifilament core and thecoated yarns prepared in the Comparative Example 5.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be obtained within the spirit and scopeof the invention.

The invention claimed is:
 1. An aqueous composition comprising: (i)porous particles present in an amount of at least 2 weight % and up toand including 10 weight %, each porous particle comprising a continuouspolymeric phase and discrete pores dispersed within the continuouspolymeric phase, the porous particles having a mode particle size of atleast 2 μm and up to and including 50 μm; (ii) a film-forming bindermaterial having a T_(g) of less than or equal to 25° C., whichfilm-forming binder material is present in an amount of at least 25weight % and up to and including 60 weight %; (iii) an inorganic fillermaterial having a value of less than 5 on the MOHS scale of mineralhardness, which non-abrasive, whitening inorganic filler material ispresent in an amount of at least 2 weight % and up to and including 15weight %; and (iv) an aqueous medium in an amount of at least 35 weight% in which the film-forming binder material is soluble or dispersible,wherein the amounts of the (i) porous particles, the (ii) film-formingbinder material, the (iii) inorganic filler material, and the (iv)aqueous medium are based on the total weight of the aqueous composition.2. The aqueous composition of claim 1, consisting essentially of the (i)porous particles, the (ii) film-forming binder material, the (iii)inorganic filler material, and the (iv) aqueous medium.
 3. The aqueouscomposition of claim 1, wherein the (iv) aqueous medium comprises waterin an amount of at least 80 weight %, based on the total weight ofsolvents.
 4. The aqueous composition of claim 1 having a viscosity of atleast 5 centipoise (0.005 Pa-sec) and up to and including 5000centipoise (5 Pa-sec) at a shear rate of 10K sec⁻¹ as measured at 25° C.5. The aqueous composition of claim 1, wherein the (iii) inorganicfiller material is a non-abrasive, whitening inorganic filler material.6. The aqueous composition of claim 1, wherein the (iii) inorganicfiller material comprises barium sulfate, calcium carbonate, mica,fluorite, clay, gypsum, or zinc sulfide.
 7. The aqueous composition ofclaim 1, wherein the (iii) inorganic filler material comprises zincsulfide.
 8. The aqueous composition of claim 1, wherein the (i) porousparticles have a mode particle size of at least 3 μm and up to andincluding 30 μm, a porosity of at least 30 volume % and up to andincluding 65 volume %, and have a continuous polymeric phase composed ofone or more of a polyester, a vinyl copolymer, and a cellulosic polymersuch as cellulose acetate, cellulose butyrate, cellulose acetatebutyrate, and cellulose acetate propionate.
 9. The aqueous compositionof claim 1, having a solids content of at least 30% and up to andincluding 65%.
 10. The aqueous composition of claim 1, wherein the (ii)film-forming binder material comprises one or more acrylic polymers. 11.The aqueous composition of claim 1, wherein the (ii) film-forming bindermaterial comprises a copolymer derived from vinyl chloride and one ormore non-halogenated acrylic monomers.
 12. The aqueous composition ofclaim 1, further containing one or more of the following optionalmaterials that are different from all of (i), (ii), and (iii):thickening agent, flame retardant, UV radiation stabilizer, tintingagent, dispersant, biocide, heat stabilizer, lubricant, and moisture ordeflection control agent, and the total amount of all of these optionalmaterials is less than 15 weight %, based on the total weight of theaqueous composition.
 13. An aqueous composition consisting essentiallyof: (i) porous particles present in an amount of at least 2 weight % andup to and including 10 weight %, each porous particle comprising acontinuous polymeric phase and discrete pores dispersed within thecontinuous polymeric phase, the porous particles having a mode particlesize of at least 3 μm and up to and including 30 μm; (ii) a film-formingbinder material having a T_(g) of less than or equal to 0° C., whichfilm-forming binder material is water-soluble or water-dispersible, andis present in an amount of at least 25 weight % and up to and including60 weight %; (iii) a non-abrasive, whitening inorganic filler materialhaving a value of less than 5 on the MOHS scale of mineral hardness,which non-abrasive, whitening inorganic filler material comprises zincsulfide and is present in an amount of at least 2 weight % and up to andincluding 15 weight %; and (iv) an aqueous medium in an amount of atleast 35 weight %, and comprises water in an amount of at least 80weight % based on the weight of total solvents, wherein the amounts ofthe (i) porous particles, the (ii) film-forming binder material, the(iii) non-abrasive, whitening inorganic filler material, and the (iv)aqueous medium are based on the total weight of the aqueous composition.14. The aqueous composition of claim 13, wherein the (i) porousparticles contain no carbon black.